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ATOMIC STRUCTURE & PHYSICAL PERIODICITY

PROPERTIES OF A CHARGED PARTICLE


For a changed particle,
Angle of deflection

Charge
Mass

ARRANGEMENT OF ELECTRONS
AROUND THE NUCLEUS

There are
PRINCIPLE QUANTUM SHELL, i.e. 1, 2, 3, 4
Electrons can be described by quantum numbers.
The principal quantum number, n , describes the main energy level of an electron.
It also indicates the relative size of the orbital and therefore relative distance of the electron
from the nucleus. The larger the value of n, the higher the energy level and the further the
electron from the nucleus.
The maximum number of electrons that can occupy each principal quantum shell is 2n2 .

Can be divided into


SUBSHELLS, ie, s, p, d, f

Number of subshells in a principal quantum shell is same as its principal quantum number.
Subshells within a given quantum shell differ slightly in energy, the energy of the subshell
increasing according to the following order: s, p, d, f

Within each subshell, there are


Orbitals
Each subshell (s, p, d, f) has one or more orbitals at the same energy level (denegetate) but
different orientations in space.
Each orbital can contain up to a maximum of 2 electrons. They must be of opposite spins.
Principal
quantum
number

2s1

Number of electrons in the


orbital
Subshell/ Type of orbital

Relationships between principal quantum shells, subshells and orbitals:


Principal quantum shell
n=1
n=2

Subshells
Orbitals
1s
one 1s orbital
2s
one 2s orbital
2p
three 2p orbitals
n=3
3s
one 3s orbital
3p
three 3p orbitals
3d
five 5d orbitals
n=4
4s
one 4s orbital
4p
three 4p orbitals
4d
five 4d orbitals
4f
seven 4f orbitals
The number of subshells in a principal quantum shell is the same as its principal quantum
number.
1

PRINCIPAL QUANTUM SHELL

Electrons can be described by 4 quantum numbers.


The principal quantum number, n , describes the main energy level of an electron.
It also indicates the relative size of the orbital and therefore relative distance of the electron
from the nucleus. The larger the value of n, the higher the energy level and the further the
electron from the nucleus.
The maximum number of electrons that can occupy each principal quantum shell is 2n2 .
All atomic orbitals of the same value n are said to be in the same quantum shell.
SUBSHELLS & ATOMIC ORBITALS

Each principal quantum shell is made up of one or more subshells.


Each subshell is in turn made up of one or more orbitals.
Relationship between subshells and orbitals:
Type of subshell

Main types of subshell


s, p, d and f

Main types of orbital:


s, p, d and f

Type & number of orbitals

contains 1 s orbital

contains 3 p orbitals

contains 5 d orbitals

contains 7 f orbitals

Orbitals

An atomic orbital is defined as the region of space with a 90% probability (or more) of finding an
electron.
The distribution of the probability of finding an electron at a certain position is the electron
density.
Each subshell (s, p, d, f) has one or more orbitals at the same energy level (degenerate) but
different orientations in space.
Each orbital can contain up to a maximum of 2 electrons. These electrons are of opposite spins.

The s Orbital

Each s subshell has only one s orbital.


All s orbitals are spherical in shape with no nodal plane (region of zero electron density).

The p Orbital

Each p subshell has three p orbitals.


The p orbital is dumb-bell in shape.
The three p orbitals in the same quantum shell are identical in size and shape but differ in their
spatial orientation.
The three p orbitals are degenerate.
2

The d Orbital

Each d subshell has five d orbitals.


They are denegerate.
ELECTRONIC CONFIGURATION

1. The Aufbau Principle

Electrons in their ground states occupy orbitals in order of energy levels.


The orbital with the lowest energy is always filled first.

2. Hund's Rule of Multiplicity

When filling subshells that contain more than one orbital with the same energy (p, d and f
subshells), each orbital must be singly occupied before electrons are paired.

3. Pauli Exclusion Principle

An orbital cannot hold more than two electrons and the two electrons sharing the same orbital
must have opposite spins.

Exceptions in Electronic Configurations

E.g. Cr: 1s2 2s2 2p6 3s2 3p6 3d5 4s1


Cu: 1s2 2s2 2p6 3s2 3p6 3d10 4s1

Explanation: Both of these configurations have a symmetrical 3d cloud of electrons which screens
the outermost electrons from the nucleus more effectively than other configuration, resulting in
lowest energy for the system.
Electronic Configuration and Periodicity

while most of the d-block elements are considered as transition metals, there are exceptions:
A transition metal is a d-block element that forms some compounds containing its ion with an
incomplete d-subshell.

d-block elements such as scandium and zinc are not considered to be transition elements:
- scandium forms only the Sc3+ which has the 3d0 configuration
3

- zinc forms only zn2+ion which has 3d10 configuration


PHYSICAL PERIODICITY
Atomic Radius
State and explain using the following:
For down the group:

Quantum shells and distance from the nucleus

For across the period:

Nuclear charge, and shielding effect, and hence effective nuclear charge
Electrostatic force of attraction between the positively charged nucleus and the outermost
electrons (whether they are pulled closer to the nucleus)

*Atomic radii across Transition Elements:

Relatively invariant
Nuclear charge increases due to increasing number of protons
Electrons are added to the inner 3d subshell, which contributes to the screening effect
Screening effect increases and nullifies, to a considerable extent, the influence of additional
proton in the nucleus
Effective nuclear charges remains almost constant

* Ionic radii (Across Periods 2 and 3)

There is a sharp increase in ionic radius from the cationic series of Na+ to Al3+ to the anionic
series of P3- to Cl-, because the anions have one more quantum shell of electrons than the
cations.
IONISATION ENERGY

First Ionisation Energy


First ionisation energy is the energy needed to remove 1 mole of electrons from 1 mole of gaseous
atoms to form 1 mole of unipositively charged gaseous ions.
X(g)

X+ (g) + e

Second Ionisation Energy


Second ionisation energy is the energy needed to remove 1 mole of electrons from 1 mole of
unipositively charged gaseous ions to form 1 mole of gaseous ions with double positive charge.

X+(g)

X2+ (g) + e

Hence,
nth ionisation energy is the energy needed to remove 1 mole of electrons from 1 mole of gaseous
ions with (n-1)+ charge to form 1 mole of gaseous ions with n+ charge.
X(n-1)+(g)

Xn+ (g) + e

Successive Ionisation Energy Values


Take note of the following in explanation:

Big increase from (n-1)th to nth ionization energy


- implies that the nth electron is from an inner quantum shell
Gradual increase and slightly greater increase
- may imply electrons came from different subshells (e.g. 2s and 2p)

Trends of First Ionisation Energy


State and explain with the following:
For trend down the group:

Number of quantum shells (and distance of outermost electron from nucleus)


Strength of the electrostatic force of attraction between nucleus and outermost electrons

For trend across the period:

Nuclear charge
Shielding effect
Effective nuclear charge
Electrostatic force of attraction between nucleus and outermost electrons

Anomalies of Ionization Energy Across Period 2 and 3

Mg

Al

The anomalies could be due to 2 possibilities:


1. Difference in subshells - e.g. Mg and Al
Mg: 1s2 2s2 2p6 3s2

Al: 1s2 2s2 2p6 3s2 3p1

The 3p subshell of Al is further away from the nucleus than the 3s subshell. There is weaker
attraction between the nucleus and the outermost electron. Less energy is required to remove the
3p electron from Al, resulting in a slower ionisation energy for Al.

2. Unpaired electrons - e.g. P and S

P: 1s2 2s2 2p6 3s2 3p3

S: 1s2 2s2 2p6 3s2 3p4

All the 3p electrons in P are unpaired. In S, two of the 3p electrons are paired. There is some
inter-electronic repulsion between the paired electrons in the 3p subshell in S. Thus less energy
than expected is required to remove one of these paired electrons from S.
First Ionisation Energy Across Transition Elements:

First ionisation energy remains relatively invariant.


1st ionisation energy involves removal of a 4s electron
Effective nuclear charge remains relatively constant across the transition series as the 3d
subshell partially shields the 4s electrons. As the nuclear charge increases across the series, the
additional d electrons shield the effect of the increasing nuclear charge.

MISCONCEPTIONS & REMARKS

Differentiate trend across period and trend across each isoelectronic series. (E.g. explain the
trend for atomic radii from Na+ to Cl-)

Shielding effect (across the period) remains relatively constant.

For electronic configurations of ions, write the electronic configuration of the neutral atom first,
and then add/remove valence electrons from the outermost shell (e.g. 4s instead of 3d)

Take note when to use the word atom and when to use the term ion

Take note when to use the term "hence lower amount of energy is required to... and "the
increase in energy needed..."

Take not of paired electrons and unpaired electrons

Inter-electronic repulsion does not just apply to nitrogen & oxygen (when comparing first IE,
etc), it applies to all Group V and adjacent Group VI elements (applies to all periods).

Note: deflection of charges/ions must not be drawn in straight lines [class test Q1]

[LT 1 Q2 (a)] When requested to draw orbitals, label the following:

Axes, e.g. z, y and x

Orbitals, e.g. 2px , 2py and 2pz

Valence electrons refer to those in the entire highest principal quantum shell. E.g. valance
electrons in N atom are those in 2s2 and 2p3 and not just 2p3. [LT Q2 (a)]

First ionization energy of period 3 atoms are lower than those in period 2. Take note of this
when drawing the graph for first I.E. [LT Q2 (b)]

It is important to state the principle quantum shell number. E.g. electrons in the 2p orbital,
not just .. in the p orbital. When the principle quantum shell number is unknown, use ns, np,
etc. [LT1 Q2 (b)]

When requested to make reference to something, e.g. electronic configuration, it must be


written out in the explanation of the answer. [LT1 Q2 (b)]